Degradable plastic composition containing amine

ABSTRACT

There is disclosed an environmentally degradable plastic composition comprising an organic polymeric material having dispersed therein at least one amine compound as a readily autoxidizable organic substance.

RELATED APPLICATIONS

This is a continuation-in-part of copending U.S. patent application Ser.No. 865,046, filed Dec. 27, 1977, which is a continuation of previouslycopending and now abandoned U.S. Pat. application Ser. No. 731,486,filed Oct. 12, 1976, which is a continuation of previously copending andnow abandoned U.S. patent application Ser. No. 288,750, filed Sept. 13,1972.

BACKGROUND OF THE INVENTION

This invention relates to novel plastic compositions having usefulphysical properties and enhanced environmental degradability.

The advent of plastics has introduced improved methods of packaginggoods. For example, polyethylene and polypropylene films, bags, andbottles, and polystyrene foam cups have the advantages of beingchemically resistant, mechanically tough, light in weight, andinexpensive. However, the increasing use of plastics in packaging hasled to the appearance of such materials in litter. While litteredplastic articles are no more objectionable than littered articles ofother materials, such as paper objects and metal cans, it has beensuggested that the impact of plastic litter can be minimized by thedevelopment of plastic materials capable of undergoing chemicaldegradation upon exposure to the natural environment.

Several approaches to the enhancement of the environmental degradabilityof plastics have been suggested. These include: (1) the incorporation ofparticulate biodegradable materials such as starch as "fillers"; (2) theintroduction of photodegradation-sensitizing groups into the molecularstructure of a polymer by copolymerization of a common monomer with asecond monomer processing such groups; and, (3) the incorporation ofsmall amounts of selected additives which accelerate oxidative and/orphoto-oxidative degradation. The last approach is particularlyattractive for the following reasons. First, the physical properties ofthe additive-containing composition are extremely similar to those ofthe base polymer. Second, existing compounding and fabrication processesand equipment can be utilized in the manufacture of finished products;hence, the cost of the finished product should be relatively low. Third,the sensitivity of the composition to environmental degradation can becontrolled by proper selection of the type and concentration ofadditive(s).

The enhancement of the rate of environmental deterioration of plasticsthrough the use of oxidation-promoting additives is known in the priorart. For example, the preparation of degradable polyolefin filmscontaining certain organic derivatives of transition metals is describedin U.S. Pat. No. 3,454,510.

While transition metal compounds are effective accelerators of oxidativeand photo-oxidative degradation processes, the use of such materials inthe preparation of useful plastic compositions having enhanceddegradability suffers from several limitations. The high reactivity ofplastic compositions containing transition metal compounds leads torapid degradation during high temperature extrusion and moldingprocesses, with the result that such processes are difficult to controland tend to produce materials having poor mechanical and chemicalproperties. Some transition metal compounds impart undesired colorationto plastic compositions into which they are incorporated. Furthermore,the toxicity of some transition metal compounds limits their utility asadditives in compositions intended for food packaging.

In accordance with this invention, the reactivity of an organic polymertoward oxidative and/or photo-oxidative degradation is significantlyenhanced by the incorporation of at least one readily autoxidizableorganic amine compound.

DESCRIPTION OF THE INVENTION

In accordance with this invention, an oxidatively degradable plasticcomposition is prepared by the admixture of an organic polymericmaterial and an amine compound as a readily autoxidizable organicsubstance.

Typical organic polymeric materials contemplated include syntheticorganic polymers (and copolymers) especially polyethylene,polypropylene, poly(1-butene), poly(4-methyl-1-pentene),ethylene-propylene copolymers, ethylene-1-butene copolymers,ethylene-1-hexene copolymers, ethylene-vinyl acetate copolymers,ethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers andtheir salts, polystyrene, rubber-modified polystyrene, styrene-butadienecopolymers, styrene-isoprene copolymers, polyvinyl chloride,poly(vinylidene chloride), polyvinyl fluoride, poly(vinylidenefluoride), polyoxymethylene, poly(ethylene oxide), poly(propyleneoxide), polyvinyl alcohol, polyvinyl acetate, polyvinyl formal,polyvinyl butyral, poly(methyl acrylate), poly(ethyl acrylate),poly(caprolactam), poly(hexamethyleneadipamide), poly(ethyleneterephthalate), vinyl chloride-vinyl acetate copolymers, celluloseacetate, cellulose propionate, cellulose acetate butyrate, ethylcellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropylcellulose, acrylonitrile polymers and copolymers, and methacrylonitrilepolymers and copolymers. Preferred polymers include organic hydrocarbonpolymers such as polyethylene, polypropylene, poly(4-methyl-1-pentene),and polystyrene.

The phrase "readily autoxidizable organic amine compound", as usedherein, may be defined as an amine substance which reacts with gaseousoxygen at a reaction rate more rapid than the corresponding reaction,under comparable conditions, of gaseous oxygen with an equal weight ofthe additive-free polymer into which the "readily autoxidizable aminecompound", is to be combined. Such reaction rates may be compared by thevolumetric measurement of the rate of absorption of gaseous oxygen byseparate pure samples of the autoxidizable substance and the polymer,under conditions of constant temperature and constant oxygen pressure.

Specific examples of organic amine compounds include benzyldimethylamine; N,N-dibenzylaniline; n-decylamine;4,4'-methylenebis-(N,N-dimethylaniline); oleylamine; linoleylamine;spermine; benzyldiethylamine; cetyldibenzylamine; cetyldimethylamine;1-dimethylamino-4-pentene; lauryl dibenzylamine; lauryl dimethylamine;linoleyldiethylamine; linoleyldimethylamine; oleyldibenzylamine;oleyldimethylamine; oleyldiethylamine; phenethylamine; piperonylamine;stearyldibenzylamine; stearyldiethylamine; stearyldimethylamine;triallylamine; tribenzylamine; tri-n-octylamine; triisopropylamine;tris(2-methylallyl)amine; N,N-diallylaniline; N,N-dibenzylmethylamine;N,N-dibenzylethylamine; N,N-dimethyl-p-toluidine; and undecenylamine.

The novel plastic compositions of this invention are prepared by anumber of methods. A preferred method consists essentially of heatingthe polymer at a temperature below its decomposition temperature,incorporating the autoxidizable substance, and mixing the ingredients soas to obtain a substantially uniform mixture. The mixture can then bemolded and cooled to form a solid molded article. In the alternative,the mixture can be extruded and cooled to form a solid extrudate.Conventional plastic processing equipment can be used for melting thepolymer, mixing the polymer with the substance(s) and molding orextruding the resulting mixture. Processing conditions, such astemperature, time, and pressure, will be obvious to those skilled in theart.

Another preferred process for preparing the novel plastic compositionsof this invention consists essentially of blending the autoxidizablesubstance with a solid polymer to obtain a substantially uniformmixture. The polymer is preferably in the form of pellets, granules orpowder. Conventional plastic processing equipment can be used in theblending operation. The processing conditions will be obvious to thoseskilled in the art. The resulting mixture can be melted at a temperaturebelow the decomposition temperature of the polymer and additive(s). Theresulting melt can be extruded or molded and cooled to form a solidextrudate or molded article.

A preferred process for preparing the novel plastic compositions of thisinvention consists essentially of casting a film from a composition ofthe autoxidizable substance and polymer in an inert solvent ordispersant. By "inert solvent" is meant that the solvent does not reactwith the polymer or autoxidizable substance. Use of this method isparticularly attractive for preparing degradable coating or adhesivematerials.

The autoxidizable substance can also be applied as a solution, slurry,or paste to the surface of a plastic article. Such surface applicationcan comprise brushing, roller coating, spraying, dipping or printing(i.e., uniformly or image-wise) on the surface of the article, in thepresence or absence of a solvent. If desired, the treated article canthen be heated to promote diffusion of the autoxidizable substance intothe polymer.

The novel plastic compositions of this invention can be prepared at thetime of disposal of conventional plastic articles. For example, aplastic article can be crushed, milled or ground, and subsequently orsimultaneously mixed with the autoxidizable substance. In the practiceof this specific embodiment, the use of readily autoxidizable wastematerials, such as wastes generated during food processing, asdegradation-promoting additives is contemplated.

In one preferred processing embodiment of the present invention, adegradable plastic composition consisting of an organic polymer and areadily autoxidizable amine compound is prepared and shaped byconventional means. The resulting film, sheet, fiber, tube or moldedarticle is subsequently treated in such a manner as to convert theplastic, via controlled partial oxidation, to a more readily degradablecomposition. This treatment may be carried out by any of severalmethods, including exposure to ultraviolet or ionizing radiation,heating in air or oxygen, surface treatment with a flame or electricaldischarge, immersion in solutions of oxidizing agents, etc. In certaincases, it may be possible to combine high temperature processing andcontrolled partial oxidation into a single step; an example would beextrusion of an oxidatively degradable plastic composition into anoxygen atmosphere.

In another preferred embodiment of the present invention, a cellulardegradable thermoplastic material is formed from a compositioncontaining a polymer, a readily autoxidizable amine substance, and ablowing agent. The blowing agent is a substance which releases asubstantial volume of gas under appropriate conditions, either bychemical decomposition to gaseous products (chemical blowing agents) orby physical vaporization (physical blowing agents). Suitable chemicalblowing agents include azodicarbonamide, azobisisobutyronitrile,4,4'-oxybis (benzene sulfonyl hydrazide), and sodium bicarbonate.Suitable physical blowing agents include nitrogen, carbon dioxide,trichlorofluoromethane and dichlorodifluoromethane. As an example, acellular (foamed) degradable plastic material may be prepared by meltingand extruding a mixture of a polyolefin, a readily autoxidizable aminematerial, and a physical blowing agent. Processing conditions similar tothose employed for the fabrication of extruded polyolefin foams lackingthe autoxidizable substance may be used. If desired, a degradablecomposite may be prepared by co-extruding a cellular degradable plasticmaterial with a non-cellular composition of the same or a differentpolymer. The latter non-cellular layer may also be modified by theincorporation of a readily autoxidizable substance. The foam orcomposite may be oriented, uniaxially or biaxially, in the course ofextrusion.

The novel environmentally degradable plastic compositions can alsocontain non-reactive additives. By the term "non-reactive additive(s)"is meant a modifying additive, filler or reinforcement commonly used inthe formulation of plastic compositions which does not materiallyinterfere with the environmental degradation process. For example, thecompositions of this invention may contain, in addition to the essentialpolymer and readily autoxidizable amine substance, such additives aslubricants, plasticizers, dyes, pigments, anti-static agents, anti-blockagents, slip agents, processing aids, adhesion promoters, flameretardants, particulate fillers, and fibrous reinforcements. Inparticular, the use of such particulate fillers and reinforcements ascalcium carbonate, talc, clays, glass, and mica is contemplated.

Antioxidants and stabilizers may also be utilized in the environmentallydegradable compositions of this invention. In some cases, it may benecessary to add an antioxidant or stabilizer to permit high temperatureprocessing, even though such additive may slow the degradation process.In other cases, it may be desirable to retard environmental degradationfor a limited period of time. The preferred antioxidant for this purposeistetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane.This composition is sold as IRGANOX 1010 by Ciba-Geigy and disclosed byU.S. Pat. Nos. 3,285,855 and 3,644,482. The antioxidant is used in anamount of about 0.001 to 0.05 percent by weight of the polymer.

It is contemplated that the degradable plastic compositions of thisinvention will ordinarily contain about 50 to 99.9% by weight of theorganic polymer, and about 50% to 0.1% by weight of the readilyautoxidizable organic amine. The quantities of any non-reactiveadditives should not be included in calculating such percentages.

In the best mode contemplated by the inventors, the composition is 99 to95% by weight low-density polyethylene and 1 to 5% by weightlinoleyldiethylamine. Low-density polyethylene has a density of lessthan 0.925 grams per cubic centimeter.

The practice of this invention is particularly suitable for preparingdegradable secondary packaging containers, such as holders or wrap forbottles and cans. Examples of such packaging articles are disclosed inthe following U.S. Pat. Nos. 3,086,651; 2,874,835; 3,750,876; 3,752,305;3,747,750; 3,016,182; 3,817,373; 3,084,792; and 3,476,237. All of theforegoing U.S. patents are incorporated by reference into this presentpatent application.

Reference is made to the drawings and the Figures thereon whichrepresent some of the best mode articles contemplated by the inventorsin the practice of this invention. These Figures and description aretaken from copending U.S. patent application Ser. No. 694,267, filedJune 9, 1976, by James E. Heider and assigned to the same assignee asthe instant application. Application Ser. No. 694,267 is incorporated byreference.

FIG. 1 is a perspective illustration of a "six-pack" of glass bottlespackaged in accordance with the present invention;

FIG. 2 is a bottom view of the package of FIG. 1;

FIG. 3 is a perspective illustration of a six-pack of cans packaged inaccordance with the present invention;

FIG. 4 is a perspective illustration of a 12-pack of glass bottlespackaged in accordance with the present invention.

Referring now to FIGS. 1 and 2 reference numeral 10 generally refers tothe cluster package of six conventional upright one-way bottles 15having similar cylindrical bodies. The containers are arranged in twoadjacent rows each having three side-by-side containers.

As can be seen in FIG. 1 the tops 12 of the bottles 15 are snuglyengaged by sleeve 11 and the bottles are contained and confined in alldirections so as to prevent relative movement of the individualcontainers within the package. FIG. 2 illustrates how the bottoms 16 ofbottles 15 are also snugly engaged by the sleeve. The heat shrunkopaque, overwrap sleeve of the invention is indicated by referencenumeral 11 and is applied so that the direction of uniaxial orientationis in the circumferential or radial direction of the sleeve. Sleeve 11is shown with decoration generally indicated by the letter "X". Suchdecoration is applied prior to wrapping the sleeve around the package.

The sealing seam of the sleeve is designated by 11a and is shown asbeing positioned on the lower side of the package. The seam is formed bythe use of adhesives or by thermally fusing edges of the sleevetogether. The seam is positioned on the side of the package as a matterof convenience and could also be located at the bottom or top of thepackage.

The open end of the sleeve 11 defines an aperture 13 which is formed asthe overlaying ends of the sleeve shrink and fuse together. The otherend of the package (not shown) has similar configuration and appearance.In forming aperture 13 there is some shrinkage in the sleeve (e.g. lessthan 10%) in the axial direction and this assists in the formation ofthe tight package.

The upper rim 13a of aperture 13 is quite functional and serves as aconvenient gripping surface for transporting the package. Due to thenature of the uniaxial orientation, rim 13a is quite strong against thestress of lifting at this point and readily supports the weight ofcontainers and their contents.

To open the package all one need do is punch a hole with the finger orother instrument through the top of the package at point between tops 12where the sleeve is tightly drawn. Such a point is generally illustratedby reference numeral 14. Once the sleeve is punctured in these areas itwill readily tear in the circumferential direction and the bottles canbe easily removed individually or in pairs. The sleeve is quiteresistant to tearing in the axial direction so the package remainsintact with respect to the remaining containers in the cluster.

FIG. 3 generally illustrates a package 20 similar to that shown in FIGS.1 and 2, except that the containers are in the form of cylindrical metalcans 21 rather than bottles. The sleeve 23 is otherwise as explainedwith respect to FIGS. 1 and 2 and is sealed together at seam 22.

FIG. 3 also illustrates how finger opening can be used with the packageof invention if desired although the finger hole is not used in thepresently preferred embodiment. Reference numeral 25 represents a fingerslit which is cut in the circumferential direction on sleeve 23. Theslit terminates in semicircular cuts 25a which serve to retard tearingin the circumferential direction upon carrying. It will be understoodthat some care must be exercised when carrying the package by fingerslits. Reference numeral 24 represents another type of circumferentialfinger slit which is formed by pushing a hot loop of wire through thesleeve. Slit 24 is sealed by beaded edges 24a which are formed bycontact with the hot wire. In practice it is likely that all the slitson one package will be of the same type.

FIG. 4 generally illustrates a 12-pack 30 of one-way bottles arranged inthree rows of four bottles each confined by sleeve 30 in tray 32. Thepackage configuration is generally the same for that shown in FIGS. 1and 2 except that the bottoms of containers 31 are set in tray 32 whichis shown as being made of corrugated fiber board. The outline of tray 32is generally seen under the sleeve 30 and comprises a flat bottom panelprovided with short upright side walls on all sides. Tray 32 is used foradded package rigidity when more than two rows of containers arepackaged to prevent relative displacement of the packaged containerswith respect to each other. Due to the use of tray 32 only the tops 34of the bottles are snugly engaged by sleeve 30 and the bottoms of thecontainers are held securely against the tray.

Although the article of manufacture of this invention has been describedand illustrated in terms of so-called secondary wrap as the best mode,this invention may also be used to make a wide variety of articlesincluding containers, particularly plastic cans and bottles.

We claim:
 1. As a composition of matter, a plastic compositionsusceptible to chemical degradation in the environment comprising anadmixture of an organic polymeric material and at least one organicamine as a readily autoxidizable organic substance substantiallyuniformly dispersed throughout said organic polymeric material.
 2. Theinvention of claim 1 wherein the degradable plastic compositioncomprises 50 to 99.9% by weight of the organic polymeric material and 50to 0.1% by weight of the autoxidizable amine.
 3. The invention of claim1 wherein the degradable plastic composition comprises 99 to 95% byweight low-density polyethylene and 1 to 5% by weightlinoleyldiethylamine.
 4. The invention of claim 1 wherein the plasticcomposition also contains 0.001 to 0.05% by weight antioxidant based onthe weight of the polymer.
 5. The invention of claim 3 wherein theplastic composition also contains 0.001 to 0.05% by weight antioxidantbased on the weight of the polyethylene.
 6. The invention of claim 5wherein the antioxidant istetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane.7. The invention of claim 1 wherein the degradable plastic compositionalso contains a blowing agent.
 8. The invention of claim 1 wherein theorganic polymeric material is a hydrocarbon polymer.
 9. The invention ofclaim 8 wherein the hydrocarbon polymer is selected from polyethylene,polypropylene, poly(4-methyl-1-pentene) and polystyrene.
 10. As anarticle of manufacture, a plastic body susceptible to chemicaldegradation in the environment comprising an admixture of an organicpolymer base and at least one organic amine as a readily autoxidizableorganic substance substantially uniformly dispersed throughout saidorganic polymer base material.
 11. The invention of claim 10 wherein theplastic body comprises 50 to 99.9% by weight of the organic polymer baseand 50 to 0.1% by weight of the autoxidizable organic amine.
 12. Theinvention of claim 10 wherein the plastic body comprises 99 to 95% byweight low-density polyethylene and 1 to 5% by weightlinoleyldiethylamine.
 13. The invention of claim 10 wherein the articleis a plastic secondary wrap for a container package.
 14. The inventionof claim 10 wherein the article is of a foamed or cellular plastic body.15. The invention of claim 10 wherein the organic polymer base is ahydrocarbon polymer.
 16. The invention of claim 10 wherein the organicpolymer is selected from polyethylene, polypropylene, poly(4-methyl-1-pentene), and polystyrene.
 17. A process for preparing aplastic composition susceptible to chemical degradation in theenvironment which comprises preparing a composition comprising anadmixture of an organic polymeric material and at least one organicamine as a readily autoxidizable organic substance and subsequentlysubjecting the prepared composition in the form of an article to anoxidizing environment.
 18. The invention of claim 17 wherein thedegradable plastic composition comprises 50 to 99.9% by weight of theorganic polymeric material and 50 to 0.1% by weight of the autoxidizableamine.
 19. The invention of claim 17 wherein the degradable plasticcomposition comprises 99 to 95% by weight low-density polyethylene and 1to 5% by weight linoleyldiethylamine.
 20. The invention of claim 17wherein the plastic composition also contains 0.001 to 0.5% by weightantioxidant based on the weight of the polymer.
 21. The invention ofclaim 17 wherein the plastic composition also contains 0.001 to 0.05% byweight antioxidant based on the weight of the polyethylene.
 22. Theinvention of claim 21 wherein the antioxidant istetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane.23. The invention of claim 17 wherein the organic polymeric material isa hydrocarbon polymer.
 24. The invention of claim 23 wherein thehydrocarbon polymer is selected from polyethylene, polypropylene,poly(4-methyl-1-pentene) and polystyrene.
 25. A process for acceleratingenvironmental degradation of an organic polymeric material comprisingdispersing substantially uniformly throughout said organic polymericmaterial at least one organic amine as a readily autoxidizable organicsubstance to form an admixture comprising said organic polymericmaterial and organic amine to form a composition and subsequentlyexposing said composition to at least one of oxygen and sunlight. 26.The invention of claim 25 wherein the degradable plastic compositioncomprises 50 to 99.9% by weight of the organic polymeric material and 50to 0.1% by weight of the autoxidizable amine.
 27. The invention of claim25 wherein the degradable plastic composition comprises 99 to 95% byweight low-density polyethylene and 1 to 5% by weightlinoleyldiethylamine.
 28. The invention of claim 25 wherein the plasticcomposition also contains 0.001 to 0.05% by weight antioxidant based onthe weight of the polymer.
 29. The invention of claim 27 wherein theplastic composition also contains 0.001 to 0.05% by weight antioxidantbased on the weight of the polyethylene.
 30. The invention of claim 29wherein the antioxidant istetrakis[methylene(3,5,-di-tert-butyl-4-hydroxyhydrocinnamate)]methane.31. The invention of claim 25 wherein the organic polymeric material isa hydrocarbon polymer.
 32. The invention of claim 31 wherein thehydrocarbon polymer is selected from polyethylene, polypropylene,poly(4-methyl-1-pentene) and polystyrene.
 33. The invention of claim 1wherein said organic amine is selected from the group consisting ofbenzyldimethyl amine; N,N-dibenzylaniline; n-decylamine;4,4'-methylenebis(N,N-dimethylaniline); oleylamine; linoleylamine;spermine benzyldiethylamine; cetyldibenzylamine; cetyldimethylamine;1-dimethylamino-4-pentene; lauryl dibenzylamine; lauryl dimethylamine;linoleyldiethylamine; linoleyldimethylamine; oleyldibenzylamine;oleyldimethylamine; oleyldiethylamine; phenethylamine; piperonylamine;stearyldibenzylamine; stearyldiethylamine; stearyldimethylamine;triallylamine; tribenzylamine; tri-n-octylamine; triisopropylamine;tris(2-methylallyl)amine; N,N-diallylaniline; N,N-dibenzylmethylamine;N,N-dibenzylethylamine; N,N-dimethyl-p-toluidine; and undecenylamine.34. The invention of claim 1 wherein said organic amine is selected fromthe group consisting of benzyldimethyl amine; N,N-dibenzylaniline;n-decylamine; 4,4'-methylenebis(N,N-dimethylaniline); oleylamine;linoleylamine; and spermine.
 35. The invention of claim 10 wherein saidorganic amine is selected from the group consisting of benzyldimethylamine; N,N-dibenzylaniline; n-decylamine;4,4'-methylenebis(N,N-dimethylaniline); oleylamine; linoleylamine;spermine benzyldiethylamine; cetyldibenzylamine; cetyldimethylamine;1-dimethylamino-4-pentene; lauryl dibenzylamine; lauryl dimethylamine;linoleyldiethylamine; linoleyldimethylamine; oleyldibenzylamine;oleyldimethylamine; oleyldiethylamine; phenethylamine; piperonylamine;stearyldibenzylamine; stearyldiethylamine; stearyldimethylamine;triallylamine; tribenzylamine; tri-n-octylamine; triisopropylamine;tris(2-methylallyl)amine; N,N-diallylaniline; N,N-dibenzylmethylamine;N,N-dibenzylethylamine; N,N-dimethyl-p-toluidine; and undecenylamine.36. The invention of claim 10 wherein said organic amine is selectedfrom the group consisting of benzyldimethylamine; N,N-dibenzylaniline;n-decylamine; 4,4'-methylenebis(N,N-dimethylaniline); oleylamine;linoleylamine; and spermine.
 37. The invention of claim 17 wherein saidorganic amine is selected from the group consisting ofbenzyldimethylamine; N,N-dibenzylaniline; n-decylamine;4,4'-methylenebis(N,N-dimethylaniline); oleylamine; linoleylamine;spermine benzyldiethylamine; cetyldibenzylamine; cetyldimethylamine;1-dimethylamino-4-pentene; lauryl dibenzylamine; lauryl dimethylamine;linoleyldiethylamine; linoleyldimethylamine; oleyldibenzylamine;oleyldimethylamine; oleyldiethylamine; phenethylamine; piperonylamine;stearyldibenzylamine; stearyldiethylamine; stearyldimethylamine;triallylamine; tribenzylamine; tri-n-octylamine; triisopropylamine;tris(2-methylallyl)amine; N,N-diallylaniline; N,N-dibenzylmethylamine;N,N-dibenzylethylamine; N,N-dimethyl-p-toluidine; and undecenylamine.38. The invention of claim 17 wherein said organic amine is selectedfrom the group consisting of benzyldimethyl amine; N,N-dibenzylaniline;n-decylamine; 4,4'-methylenebis(N,N-dimethylaniline); oleylamine;linoleylamine; and spermine.
 39. The invention of claim 25 wherein saidorganic amine is selected from the group consisting ofbenzyldimethylamine; N,N-dibenzylaniline; n-decylamine;4,4'-methylenebis(N,N-dimethylaniline); oleylamine; linoleylamine;spermine benzyldiethylamine; cetyldibenzylamine; cetyldimethylamine;1-dimethylamino-4-pentene; lauryl dibenzylamine; lauryl dimethylamine;linoleyldiethylamine; linoleyldimethylamine; oleyldibenzylamine;oleyldimethylamine; oleyldiethylamine; phenethylamine; piperonylamine;stearyldibenzylamine; stearyldiethylamine; stearyldimethylamine;triallylamine; tribenzylamine; tri-n-octylamine; triisopropylamine;tris(2-methylallyl)amine; N,N-diallylaniline; N,N-dibenzylmethylamine;N,N-dibenzylethylamine; N,N-dimethyl-p-toluidine; and undecenylamine.40. The invention of claim 25 wherein said organic amine is selectedfrom the group consisting of benzyldimethylamine; N,N-dibenzylaniline;n-decylamine; 4,4'-methylenebis(N,N-dimethylaniline); oleylamine;linoleylamine; and spermine.